CA2247431A1 - Adhesive compositions including polyvinylpyrrolidone, acrylic acid polymers, and polyamines - Google Patents
Adhesive compositions including polyvinylpyrrolidone, acrylic acid polymers, and polyamines Download PDFInfo
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- CA2247431A1 CA2247431A1 CA002247431A CA2247431A CA2247431A1 CA 2247431 A1 CA2247431 A1 CA 2247431A1 CA 002247431 A CA002247431 A CA 002247431A CA 2247431 A CA2247431 A CA 2247431A CA 2247431 A1 CA2247431 A1 CA 2247431A1
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- composition
- containing polymer
- acrylic acid
- polyvinylpyrrolidone
- amine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
- A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
- A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
- A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
- A61K9/7053—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds, e.g. polyvinyl, polyisobutylene, polystyrene
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
- A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
- A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
- A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
- A61K9/7053—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds, e.g. polyvinyl, polyisobutylene, polystyrene
- A61K9/7061—Polyacrylates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
- A61L15/585—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S206/00—Special receptacle or package
- Y10S206/813—Adhesive
Abstract
A composition comprising a cross-linked salt of (a) a polyvinylpyrrolidone having ring opened pyrrolidone groups; (b) at least one acrylic acid-containing or methacrylic acid-containing polymer; and (c) an amine-containing polymer. The composition may be used as a pressure-sensitive adhesive, has good tack, and may be peeled from the body or from an object without causing damage or injury to the body or object.
Description
W 097133645 PCT~US97/~3402 ~iDEU3SI~nE COMPOS~T~O~S IN~LUDING PoLyvlNy~pyR~oT-AC:E~YI.IC ~-CID POLYJIERS, AND POLVAMT?~2.~
~ his invention relates to adhesives and, in particular, to hydrogel pressure-sensitive adhe~ives. More particularly, this i~vention relates to adhesives which include a polyvinylpyrrolidone, an acrylic acid polymer, and a polyamine. Such adhesives contain only a min;m water, yet do not dry out.
Pressure-sensitive adhesives have a variety of application~, includir.g uses in wound and burn dres~ings, bandage~, surgical drape~, plasters, trans~erm~l drug delivery systems, antimicrobial barriers for catheter hubs, and ostomy pro~ucr 5 Where the pressure sensitive hydrogel also cont~;n~
electrolyte that imparts conductivity, the pressure sensitive hydrogel can be used for electrode~, ~or an~i-static closure strips ~or electronic packaging, anti-static ~ticky mats for clean room~, and for attaching photographic or X-ray film to splr.dles of f ilm canisters.
U.S. Patent No. 5,306,504 discloses an adhesive hydrogel compositicn having a high water content, and which comprises a cross-linked ampholytic salt o~ a high molecular weight water-soluble polyvinylpyrrolidone having ring opened pyrrolidone groups, and a water-soluble amine-con~; ni n~ polymer. The polyvinylpyrrolidone has ring opened pyrrolidone groups providing at least 1.5x10-2 milli-e~uivalents of carboxylic acid groups per gram of polymer.
The amine-cont~ining polymer may be polyethyl~neimine, amine-terminated po~yethyleneoxide, or amine-terminated polyethylene oxide/polypropylene oxide.
S~Jtx:~ 1 1 1 UTE SHEET (RULE 26) Such an adhesive, however, ha~ a tack, or a stickin~ss, which is less than that desired for certain applications, such as, for example, as a wound dressing for moi~t or damp skin or as a closure strip for packaging of electronic components. Thus, it is an object of the present invention to provide an adhesive having an increased tack yet remain readily peelable from the body or ~rom the object to which it is adhered, and which has improved adhesion to wet skin.
In accordance with an aspect of the present invention, there is provided a composition which comprises a cross-l;nke~ salt o~ (a) a polyvinylpyrrolidone having ri}lg opened pyrrolidone groups; (b) at least one acrylic acid-cont~;n;ng polymer or methacrylic acid-containiny polymer;
and ~c) an amine-cont~in;ng polymer.
In one embodiment, the polyvinylpyrrolidone has ring opened pyrrolidone groups which provide at least 1.5xln-2 milliequivalents of carboxylic acid groups per gram of polymer, preferably at least 1.7 x 10-Z millie~uivalents of c~hoxylic acid groups per gram of polymer. Higher levels of ring opened pyrrolidone groups provide a greater number of cross-links; however, the level should not be so high as to re~ult in significant cross-linking of the polyvinylpyrrolidone with itself. Ring opening of pyrrolidone groups of the polyvinylpyrrolidone may be accomplished by means known to those skilled in the art, such as by treatment in aqueous solution at elevated temperature with a weak acid (such as acetic acid), or with a base, such as sodium hydroxide.
In a preferred embo~ nt, the polyvinylpyrrolidone has a high molecular weight. In one embodiment, the polyvinylpyrrolidone has a K-value of at least 30, preferably at least 50. In general, the K-value does not exceed 120. Preferably, the K-value is from about 75 to about 95. As is well known, K-values as assigned to polyvinylpyrrolidone represent a function o~ the average SUBSTITUTE Sl ._._1 (RULE 26) W O 97/33645 PCTrUS97/03402 molecular weight. K-values are derived ~rom viscosity mea~ ..e~lts and are calculated according to Fikentscher's formula.
Acrylic acid-cont~;ning polymers or methacrylic acid-cont~;n;n~ polymers which may be employed include, but are not limited to, acrylic acid or methacrylic acid homopolymers, copolymers of acrylic acid or methacrylic acid and acrylic acid esters or methacrylic acid esters, and acrylic acid-cont~in-ng or methacrylic acid-co~t~;n;ng terpolymers, such as terpolymers including acrylic acid and acrylic acid esters and terpolymers of acrylic acid or methacrylic acid, butadiene, and styrene. In general, the acrylic acid-cont~in~n~ or methacrylic acid-cont~,ni~
polymer has adhesive properties.
In a preferred embodiment, the at least one acrylic acid-con~A;n~ng polymer or methacrylic acid-cont~in;ng polymer i~ a polymer including an acrylic acid moiety or methacrylic acid moiety and at least one other moiety.
Pre~erably, the at least one other moiety is water-insoluble.
In another embo~;m~nt, the at least one acrylic acid-cont~in;ng or methacrylic acid-cont~in;ng polymer is a copolymer of acrylic acid or methacrylic acid and an acrylic acid ester or methacrylic acid ester. In one embodiment, the ester is an acrylic acid ester. Acrylic acid esters which may be employed include, but are not limited to, ethyl acrylate, butyl acrylate, octyl acrylate, and 2-ethyl hexyl acrylate. The at least one acrylic-acid ~nt~;n;ng polymer which is employed in the composition, in one embodiment, may be a combination of two or more acrylic acid-cont~; ni ng copolymers of acrylic acid and the above-mentioned acrylic acid esters. In general, such copolymer has a molecular weight of from about 10,000 to about 5,Q00,000, preferably ~rom about I0,000 to about 200,000.
In another preferred embodiment, the acrylic acid-cont~;n;ng polymer is a terpolymer including acrylic acid and two acrylic acid esters. The acrylic acid esters may be selected from those hereinabove described. In one SU~Il~TE SHEET (RULE 26) W O 97/33645 PCT~US97/03402 embodiment, the terpolymer is a terpoly~er of acrylic acid, butyl acrylate, and 2-ethyl hexyl acrylate. Examples of such terpolymer5 are sold by ~on~Anto as Gelva 2333, Gelva 2397, and Gelva 2484.
In another embodiment, the at least one acrylic acid-~nt~;n;ng or methacrylic acid-cont~;n;ng polymer is a terpolymer of acrylic acid or methacrylic acid, butadiene, and styrene.
In a preferred embo~;m~nt, the acrylic acid-contAin;n~
polymer or methacrylic acid-cont~ining polymer, prior to m; X; ng with the polyvinylpyrrolidone and the amine-contAining polymer, is in the form of an emulsion. More preferably, the acrylic acid-contAin;ng polymer or methacrylic acid-cont A; n; ng polymer is in the ~orm of an emulsion of a copolymer of acrylic acid or methacrylic acid and acrylic acid esters or methacrylic acid esters.
Amine-contA;ning polymers which may be included in the composition include, but are not limited to, polyethylf~nf~i m; ne, amine-terminated polyethylene oxide, amine-terminatedpolyethylene/polypropyleneoxide,polyme~s of dimethyl amino ethyl methacrylate, and copolymers of dimethyl amino ethyl methacrylate and vinyl pyrrolidone.
In one embodiment, the amine-contA;n;ng polymer is polyethylF~n~; m; ne. In general, the polyethyl~ne; m; ne has a molecular weight of from about 2~,000 to about 750,000, preferably from about 70,000 to about 750,000.
In general, the preparation of the adhesive composition takes place in an aqueous medium, whereby a~ueous solutions o~ the polyvinylpyrrolidone and the amine-c~nt~;n~n~ polymer are mixed with the emulsion ~ont~;n;ng the acrylic acid-contA;n;ng or methacrylic acid-contA; n; ng polymer. Although the scope of the present invention is not to be limited to any theoretical reasoning, it is believed that the acid moieties in the acrylic acid-containing or methacrylic acid-contA;n;ng polymer become co-crosslin~ed with the polyvinylpyrrolidone by the amine-contAi n~ ny polymer. Such reaction also is a competition reaction between the acid groups of the ring Sl.~vS 111 ~JTE SHEET (RULE 26) WO 97133645 PCT~US97/03402 opened polyvinylpyrrolidone an~ the acid group~ o~ the acrylic acid-containing polymer or methacrylic acid-con~;nln~ polymer with the amine-cont~;n;ng polymer. In addition, the addition o~ the acrylic acid-cont~tn~ng polymer slows the rate of gelation of the polyvinylpyrrolidone by the polyamine. Thus, gelation of the resulting composition occurs over a period of minutes, a~ opposed to an almost instantaneous gelation. Therefore, one may use conventional coating equipment for forming the adhesive composition, and then drying the product.
The polyvinylpyrrolidone, acrylic acid-cont~in;n~
polymer or methacrylic acid-cont~n~ng polymer and amine-cont~;n~ng polymer are present in amounts which enable co-cro~glinking of the acid moieties of the polyvinylpyrrolidone and of the acrylic acid-cont~, n; n~
polymer or methacrylic acid-cont~in;ng polymer with the amine-~ntAln;ng polymer. In general, the polyvinylpyrrolidone and amine-cont~;n;ng polymer are present in the composition at a weight ratio o~
polyvinylpyrrolidone to amine-cont~;n;ng polymer of ~rom about 40:1 to 150:1, pre~erably ~rom about 60:1 to about 80:1, and the acrylic acid-cont~in;ng polymer or methacrylic acid-cont~;ning polymer is present in the composition at a weight ratio of polyvinylpyrrolidone to acrylic acid-cont~in~ng polymer or methacrylic acid-cont~; n; ng polymer of from about 8:1 to about 16:1, preferably from about 10:1 to about 16:1. Upon mixing of the above-mentioned components, an adhesive composition is formed which is not soluble in water, yet is capable of ab~orbing from about 3 to 10 times its own weight in water when dried. Such composition has improved tack or stickiness. The composition has a cohesiveness to itself which is greater than the adhesiveness to the object or body to which it is adhered. Thus, the adhesive may be peeled readily ~rom the object or the body without damage or injury to the object or body.
S~l~S 11 ~ ~JTE SHEET (RULE 26) W O 97/3364S PCTrUS97/03402 In one embodiment, the compo~ition ~urther includes a plasticizer. Examples of plasticizers which may be employed include, but are not limited to, polyalkylene glycols such as polyethylene glycol and glycerine. Such plasticizers prevent drying of the adhesive and increase the tack. In one embodiment, the plasticizer is polyethylene glycol. The polyethylene glycol may have a molecular weight of ~rom about 100 to about 600, preferably at about 300. The polyethylene glycol typically has a melting point o~ from about 20~C to about 25~C at a molecular weight of 600, and has a melting point below -10~C at a molecular weight of 300. In general, the polyethylene glycol is added at a ratio of polyvinylpyrrolidone/polyethylene glycol of from about 0.5:1 to about 2:1, preferably from about 0.8:1 to about 1 : 1 .
In another embo~m~nt, the composition further includes a water-soluble tackifier. Examples of water-soluble tacki~iers which may be employed include, but are not limited ~o, polyvinylethers such as polymethylvinylether and polyvinylpyrrolidone having no ring opened groups.
In yet another embodiment, the composition may further include a surfactant, such as a phospholipid surfactant or other surfactants that provide antibacterial stabilizing propertie~ to the composition.
The composition of the present invention is useful in a wide variety o~ systems involving application to ~ni~l bodies, including especially human bodies. These include medical systems such as an adhesive for surgical drape~, wound and burn dressings and packings, bandages, plasters, transdermal drug delivery devices, and antimicrobial barriers for catheter hubs.
In a wound or burn dressing or packing, for example, in addition to the incorporation of a plasticizer and ~urfactant in the composition, the product may also contain a bactericide such as chlorhexidine gluconate, silver or copper compounds l-ke silver sulfadiazine, silver apacide SU~Ill~TE SHEET(RULE 26) W O 97/33645 PCT~US97/03402 and copper apaci~e, or an antibiotic or other ~nt;m;cro~ial The composition may also cont~;n enough sodium chloride to match physiological saline in order to prevent osmotic pumping ~rom the wound, and agents to promote regrowth of tissue. Wound or burn dressings and packings generally involve a releasable thermally ~ormed plastic receptacles ~or holding the compo~ition and a polymeric film, suc~ as polyurethane film, backing to control moisture-vapor transmission.
The composition may be used to attach a medical device to the body. In this case the aqueous gel may cont~i n, in addition to the tacki~ying plasticizer, an ~nt;m;crobial agent. When used as an adhesive to attach a catheter, such as a central venous catheter or intravenous catheter, it cover~ the hub providing an antimicrobial barrier to in~ection. The tacky composition may also be used to attach ostomy products to the body In a transdermal drug delivery system, the composition of the present invention will cont~ i n, in addition to the plasticizer, skin absorption agents like alcohols and amides, and at least one bioef~ecting drug. Examples of drugs that may be incorporated in such a system are nitroglycerine, pilocarpine, scopo- ~m; ne, clonidine, ~entanyl, nicotine, fen~luramine, phenterimine, phenylpropanolamine, theophylline, lidocaine, benzocaine, capsaicin, nicotinates, ergotamine tartrate, miconazole nitrate, salicylates such as choline salicylate, methyl salicylate, and the like. Such drugs may be added to the composition in an amount up to about 10~ by weight.
An electrolyte salt may be included in the composition to render it conductive for use in attaching electrocardiogram electrodes, transcutaneous electrical nerve stimulator electrodes, electro-surgical unit electrodes, bio-~eedback electrodes and iontophoresis drug delivery electrodes and de~ibrillation pads. Potassium chloride, sodium chloride sodium acetate, and magnesium acetate are examples o~ suitable electrolyte salts. Such ~alts may be present in the composition in an amount SUBSTITUTE SHEET (RULE 25) W O 97/33645 PCTrUS97/03402 between about 1 and about 20~, by weight, preferably about 2 and about 10~. The electrolyte salt may be incorporated in the reaction mixture at or about the time~that the ring opened PVP and amine-cont~i ni n~ polymer are mixed, preferably as by adding it to the water prior to dissolving the ring opened PVP. The conductive composition may al~o cs~t~n bioeffec~ive material for iontophoresis drug delivery.
In addition, the electrolyte ~alts herP~n~hove descri~ed, as well as carbon black or metal powders ~uch as copper powder, may be included in the adhesive composition to ~orm a conductive adhesive, a static dissipative adhesive, or an anti-static adhesive for closure strips for the packaging of sensitive electronic components such as computer chips, for example, or of photographic and x-ray films. Such compo~itions possess ade~uate conductivity as well as good adhesiveness. Such an adhesive yet conductive composition also may be employed in clean room dirt removal mats, whereby the adhesive fonms the top surface of the clean room mat, and retains dirt particles and metal particles.
The invention now will be described with respect to the examples; however, the scope of the present invention i8 not intended to be limited there}:)y.
Example 1 A two-part system was made of Part A and Part B. Part A contained 50.35g of a 20~ wt./wt. polyvinylpyrrolidone solution (with ring opened pyrrolidone groups), 3.0g pota~sium chloride, 24g SDA40 ethyl alcohol and 1.25g Gelva A~ 259, which is an acrylic polymer but not having any acid groups present. Part B consisted of 12.0g polyethyle~e glycol 300, 21.1g SDA40 ethyl alcohol, and 1.40g of a 12.5~
solids solution of polyethyl~n~;m;nP. The two parts were added to each other, mixed rapidly, and poured in the nip of a knife coater which had a release liner and a gap setting of 21 mils. Before the liner wa~ pulled through fully, the gel had formed. The coated liner was then dried in an oven with high air flow at 110~C. The dried product SUt~S ~ JTE SHEET (RULE 26) W O 97/33645 PCTrUS97/03402 wa~ 2 mils thick, had good dry tack and had resistance of 10 ohms. The ~ilm, however, was not uni~orm because it gelled before being pulled through the nip.~
~ Example 2 A two-part ~ystem was made o~ Part A and Part B. Part A cont~1 n~ 50.41g of a 20~ polyvinylpyrrolidone solution wt/wt., 20g of SDA40 ethyl alcohol, 3.0g potassium chloride, and 1.30g o~ Gelva 2484 (an acid co~t~in;n~
acrylic acid ester adhesive) emulsion. Gelva 2484 is an acrylic acid ester and acrylic acid-cont~;n~ng terpolymer from Monsanto including acrylic acid, butyl acrylate, and 2-ethyl hexyl acrylate. Part B consisted of 12.12g polyethylene glycol 300, 20g of S~A40 ethyl alcohol and 1.27g of 12.5~ polyethylene~m;n~ solution. The two parts were combined, mixed and poured into the nip of a knife over roller coater in which wa~ a release liner, gap set ~or 21 mils. The liner was pulled through the coater.
After removal, excess coating dripped for about 15 seconds ~efore gelation started. The coating on the release liner was dried in an oven with high air flow at 110~C for 5 minutes. The resulting 2 mil coating had excellent d~y tack and good resistivity.
Example 3 A two-part system was made of Part A and Part B. Part A cont~;ne~ 50.35g 20~ polyvinylpyrrolidone solution, 3g pota~sium chloride, 25g S~A40 ethyl alcohol and 1.30g Gelva 2397 adhesive, which is an acrylic acid ester and acrylic acid-cont~ n; ng terpolymer having the compo~Pnt~
here;n~hove described, and which has a higher acrylic acid content that Gelva 2484. Part B contained 12.12g polyethylene glycol 300, 1.27g 12.5~ polyethylen~;m;n~
solution, and 20g SDA40 ethyl alcohol. Parts A and B were combined, mixed and poured into the nip of a knife over a roll coater which had a release liner in the nip. The release liner was pulled through and the excess material dripped for more than 30 seconds before gelation started.
SUBSTITUTE SHEET (RULE 26) W O 97/33645 PCT~US97/03402 The coating was dried in an oven with high air ~low at 110~
~or 5 minutes. The 2 mil coating had excellent tack a~d resi~tivity.
Example 4 A two-part system was made of Part A and Part B. Part A consisted of a mixture which was in a ratio of 50.34g 20 polyvinylpyrrolidone (with partial ring opened groups~, 25.31g SDA40 ethyl alcohol and 1.30g Gelva 2333 adhesive (an acrylic adhesive, including an acrylic acid ester alld acrylic acid-cont~n;ng terpolymer having the components here;n~hove described, with an acid content between Gel~a 2484 and Gelva 2397), and 3g of potassium chloride. Part B was a mixture of 12.17g polyethylene glycol 300, 1.27g of a 12.5~ solution o~ polyethyl~n~neim~ne and 20.21g SDA40 ethyl alcohol. The solutions of both parts were placed in separate tanks and were ed separately by two gear pumps to a static mixer (3 elements, 2~" long, 5/8" thick). The combined mixture was fed to the nip of a roll coater with a spreader bar through which a ~on~l~ctive release liner was passing. The width o~ the coater is 14" after the coater it went into a dryer oven with 3 zone heating and good air flow. The liner was be ng pulled at about 50 ~t/min. At the exit of the dryer a second "easy release" liner was placed over the dried adhesive. The 14" wide web was slit to 3" wide and tested as a sealing tape ~or a package ~or elertronic chips. It was ~ound to have good adhesive properties and to pre~ent static charge build-up.
Example 5 A two-part system was made o~ Part A and Part B. Part A cont~; n~ 50.35 gms of a 20~ polyvinylpyrrolidone with some ring opened pyrrolidone groups, 24gms SDA40 ethyl alcohol, 1.03gms o~ a 33% solution o~ polyvinyl methylether and 1.25gms o~ Gelva AE259. Part B cont~; nP~ 12.0g~s polyethylenglycol, 25 yms of SDA40 ethyl alcohol, and 1.30gms 12.5% polyethyleneimine. The two parts were mixed together, ~tirred, and then q~ickly poured into the nip of a kni~e over a roll coater with a gap of 21 mils and in which a release liner was placed. The liner was pulled SU~5 1 1 1 UTE SHEET [RULE 26) through the gap and gelation occurred in the process o~
pulling. The coating on the release liner was placed in an oven with high air fiow and heated at 110~C - It was dried ~or 15 minutes. A~ter cooling it was tested for dry and wet tack. It had adequate dry tack but poor wet tack. The coating appeared to be non-uniform.
This illustrate~ the ~onmation of a pressure-sensitive adhesive that does not contain any free acid groups in the backbone of the acrylic acid-cont~;ng polymer.
Example 6 A two-part system was made of Part A and Part B. Part A cont~;n~ 50.41g of a 20~ polyvinylpyrrolidone solution (cont~n;n~ ring opened pyrrolidone groups) 22grams of SDA40 ethyl alcohol, 1.30 grams of Gelva 2484, and 1.24g of a 20% solution of po~ymethylvinylether in water. Part B
co~t~;nPd 12.18g polyethylene glycol 300, 23 grams of SD~40 ethyl alcohol, and 1.10 grams of 12.5~ polyethyl~ne;m;ne.
The two parts were com~ined, stirred and poured into the nip of a knife over a roller coater set at 21 mil gaps in which was a release liner. The liner with the coating was pulled through. Excess coating began to drip tl,. ouyh the gap and after about 15 seconds began to gel.
The liner with the coating was placed in an oven with high air flow at 110~C ~or 15 minutes. After cooling it wa~ lAm;n~ted to a thin film polyurethane o~ about 1 mil thickness. Samples were tested by ~e~nvving the release liner from strips and dry and wet tack were determined.
The sample was equivalent in dry tack to ~xample 5 ~ut had much better wet tack.
Exam~le 7 A two-part system was made 0c Part A and Part B. Part A cont~;nP~ 50.35 gram~ of 20~ polyvinylpyrrolidone, 23.60 grams SDA40 ethyl alcohol, ~.30 grams Gelva 2397 emulsion adhesive cont~i n; ng unneutralized acid groups in the backbone, and 1.56g of a 20~ solution of polymethylvinylether in water. Part B contained 12.12 grams of polyethylene g ycol 300, 20 grams of SDA40 ethyl alcohol and 1.01 grams of a 12.5~ polyethyl~ne~m;ne in SUBSTITUTE SHEET(RULE 26) W O 97/33645 PCTrUS97/03402 water. Part B was added to Part A and ~uickly stirred and ~e~ to the nip o a knife over a roll coater with a gap of 21 mils in which was a release liner. The liner was pulled through the gap depositing a film of the coating.
After removal, excess coating dripped from the gap and did not start to gel for about 1 minute. The liner with the coating was placed in an o~en with high air ~low at 110~C
~or 15 minutes. After removal it was allowed to cool and then ~Am;n~ted to a polyurethane film. A stAn~Ard peel adhesion of this Eilm with adhesive against stainless steel was measured at 350-500 grams. It had good adhesion to wet skin but was painlessly peeled from the skin.
Example 8 A two-part system was made of Part A and Part B. Part A contained 49.~3 grams 20% polyvinylpyrrolidone with partial ring opened pyrrolidone groups, 25.09g SDA40 ethyl alcohol, and 1.58g Gelva 2333 emulsion adhesive. Part B
cont~n~A 1.27g polyethyl~ne;~n~, 20.79g SDA40 ethyl alcohol and 8.85g polyethylene glycol 300. Part B was added to Part A, stirred and then ~uickly added to the nip of a knife over a roller coater, having a gap o~ 21 mils with a release liner in the gap. The release liner wa~
pulled through and after it cleared the gap excess coating began dripping down. After a~out 30 seconds the coating solution began to gel. Ti1e coating on the release liner was placed in an oven with high air ~low and at a temperature o~ llO~C. A~ter 15 minutes the liner with the coating was removed and allowed to cool. It was lAm~nAted to a thin ~ilm urethane. It had good adhesion to the urethane film. Testing of the film lAm~nAted adhesive showed it had good adhesion to wet or damp skin but did not have as good d~y tack as in Example 7.
Example 9 S~ 111 ~JTE SHEET (RULE 26) W O 97/3364~ PCTAUS97/03402 ~ ach of Formulations A, B, and C were made, havinq the ~ollowing components:
Part A
50g ~ 20% polyvinylpyrrolidone 48g H2O
1.3g 20~ polymethylvinylether (PVM) in water 0.08g sodium C14-C16 olefin sulfonate surfactant Part B
12g polyethylene g~ycol 12g H2O
l.Og 12.5~ polyethylPne~m7ne in H20 Formulation A had no adhesive com~onent added. Formulation B ~urther included 1.3g of Gelva 2484 in Part A.
Formulation C further included 1.3g of Gelva 2333 in Part A.
For each formulation, Part ~ was added to Part A, and each ~ormulation was stirred. Subsequent to stirring, each fonmulation was poured onto an interface of a wire wound stainless steel rod and glass. The rod then is rolled along the glass sur~ace as the formulation is being applied, thereby ~orming a coating o~ each ~ormulation on a glass sur~ace. Each o~ Formulations A, B, and C then was dried at 105~C ~or 15 minutes, and then covered with a polye~ter film. One-inch stxips then were cut, and the adhesion of polyester to glass for each ~ormulation was measured. The adhesion for each formulation was as follow~:
Formulatio7l A - 1.1 oz./in.
Fonmulatio~ B - 3.7 oz./in.
Formulation C - 4.5 o~./in.
It is to be understood, however, that the scope of the present invention is not to be limited to the speci~ic embodiments described above. The invention may be practiced other than as particularly described above. The invention may be practiced other than as particularly described and still be within the scope of the accompanying claims.
S~DBSTITUTE SHEET (RULE 26)
~ his invention relates to adhesives and, in particular, to hydrogel pressure-sensitive adhe~ives. More particularly, this i~vention relates to adhesives which include a polyvinylpyrrolidone, an acrylic acid polymer, and a polyamine. Such adhesives contain only a min;m water, yet do not dry out.
Pressure-sensitive adhesives have a variety of application~, includir.g uses in wound and burn dres~ings, bandage~, surgical drape~, plasters, trans~erm~l drug delivery systems, antimicrobial barriers for catheter hubs, and ostomy pro~ucr 5 Where the pressure sensitive hydrogel also cont~;n~
electrolyte that imparts conductivity, the pressure sensitive hydrogel can be used for electrode~, ~or an~i-static closure strips ~or electronic packaging, anti-static ~ticky mats for clean room~, and for attaching photographic or X-ray film to splr.dles of f ilm canisters.
U.S. Patent No. 5,306,504 discloses an adhesive hydrogel compositicn having a high water content, and which comprises a cross-linked ampholytic salt o~ a high molecular weight water-soluble polyvinylpyrrolidone having ring opened pyrrolidone groups, and a water-soluble amine-con~; ni n~ polymer. The polyvinylpyrrolidone has ring opened pyrrolidone groups providing at least 1.5x10-2 milli-e~uivalents of carboxylic acid groups per gram of polymer.
The amine-cont~ining polymer may be polyethyl~neimine, amine-terminated po~yethyleneoxide, or amine-terminated polyethylene oxide/polypropylene oxide.
S~Jtx:~ 1 1 1 UTE SHEET (RULE 26) Such an adhesive, however, ha~ a tack, or a stickin~ss, which is less than that desired for certain applications, such as, for example, as a wound dressing for moi~t or damp skin or as a closure strip for packaging of electronic components. Thus, it is an object of the present invention to provide an adhesive having an increased tack yet remain readily peelable from the body or ~rom the object to which it is adhered, and which has improved adhesion to wet skin.
In accordance with an aspect of the present invention, there is provided a composition which comprises a cross-l;nke~ salt o~ (a) a polyvinylpyrrolidone having ri}lg opened pyrrolidone groups; (b) at least one acrylic acid-cont~;n;ng polymer or methacrylic acid-containiny polymer;
and ~c) an amine-cont~in;ng polymer.
In one embodiment, the polyvinylpyrrolidone has ring opened pyrrolidone groups which provide at least 1.5xln-2 milliequivalents of carboxylic acid groups per gram of polymer, preferably at least 1.7 x 10-Z millie~uivalents of c~hoxylic acid groups per gram of polymer. Higher levels of ring opened pyrrolidone groups provide a greater number of cross-links; however, the level should not be so high as to re~ult in significant cross-linking of the polyvinylpyrrolidone with itself. Ring opening of pyrrolidone groups of the polyvinylpyrrolidone may be accomplished by means known to those skilled in the art, such as by treatment in aqueous solution at elevated temperature with a weak acid (such as acetic acid), or with a base, such as sodium hydroxide.
In a preferred embo~ nt, the polyvinylpyrrolidone has a high molecular weight. In one embodiment, the polyvinylpyrrolidone has a K-value of at least 30, preferably at least 50. In general, the K-value does not exceed 120. Preferably, the K-value is from about 75 to about 95. As is well known, K-values as assigned to polyvinylpyrrolidone represent a function o~ the average SUBSTITUTE Sl ._._1 (RULE 26) W O 97/33645 PCTrUS97/03402 molecular weight. K-values are derived ~rom viscosity mea~ ..e~lts and are calculated according to Fikentscher's formula.
Acrylic acid-cont~;ning polymers or methacrylic acid-cont~;n;n~ polymers which may be employed include, but are not limited to, acrylic acid or methacrylic acid homopolymers, copolymers of acrylic acid or methacrylic acid and acrylic acid esters or methacrylic acid esters, and acrylic acid-cont~in-ng or methacrylic acid-co~t~;n;ng terpolymers, such as terpolymers including acrylic acid and acrylic acid esters and terpolymers of acrylic acid or methacrylic acid, butadiene, and styrene. In general, the acrylic acid-cont~in~n~ or methacrylic acid-cont~,ni~
polymer has adhesive properties.
In a preferred embodiment, the at least one acrylic acid-con~A;n~ng polymer or methacrylic acid-cont~in;ng polymer i~ a polymer including an acrylic acid moiety or methacrylic acid moiety and at least one other moiety.
Pre~erably, the at least one other moiety is water-insoluble.
In another embo~;m~nt, the at least one acrylic acid-cont~in;ng or methacrylic acid-cont~in;ng polymer is a copolymer of acrylic acid or methacrylic acid and an acrylic acid ester or methacrylic acid ester. In one embodiment, the ester is an acrylic acid ester. Acrylic acid esters which may be employed include, but are not limited to, ethyl acrylate, butyl acrylate, octyl acrylate, and 2-ethyl hexyl acrylate. The at least one acrylic-acid ~nt~;n;ng polymer which is employed in the composition, in one embodiment, may be a combination of two or more acrylic acid-cont~; ni ng copolymers of acrylic acid and the above-mentioned acrylic acid esters. In general, such copolymer has a molecular weight of from about 10,000 to about 5,Q00,000, preferably ~rom about I0,000 to about 200,000.
In another preferred embodiment, the acrylic acid-cont~;n;ng polymer is a terpolymer including acrylic acid and two acrylic acid esters. The acrylic acid esters may be selected from those hereinabove described. In one SU~Il~TE SHEET (RULE 26) W O 97/33645 PCT~US97/03402 embodiment, the terpolymer is a terpoly~er of acrylic acid, butyl acrylate, and 2-ethyl hexyl acrylate. Examples of such terpolymer5 are sold by ~on~Anto as Gelva 2333, Gelva 2397, and Gelva 2484.
In another embodiment, the at least one acrylic acid-~nt~;n;ng or methacrylic acid-cont~;n;ng polymer is a terpolymer of acrylic acid or methacrylic acid, butadiene, and styrene.
In a preferred embo~;m~nt, the acrylic acid-contAin;n~
polymer or methacrylic acid-cont~ining polymer, prior to m; X; ng with the polyvinylpyrrolidone and the amine-contAining polymer, is in the form of an emulsion. More preferably, the acrylic acid-contAin;ng polymer or methacrylic acid-cont A; n; ng polymer is in the ~orm of an emulsion of a copolymer of acrylic acid or methacrylic acid and acrylic acid esters or methacrylic acid esters.
Amine-contA;ning polymers which may be included in the composition include, but are not limited to, polyethylf~nf~i m; ne, amine-terminated polyethylene oxide, amine-terminatedpolyethylene/polypropyleneoxide,polyme~s of dimethyl amino ethyl methacrylate, and copolymers of dimethyl amino ethyl methacrylate and vinyl pyrrolidone.
In one embodiment, the amine-contA;n;ng polymer is polyethylF~n~; m; ne. In general, the polyethyl~ne; m; ne has a molecular weight of from about 2~,000 to about 750,000, preferably from about 70,000 to about 750,000.
In general, the preparation of the adhesive composition takes place in an aqueous medium, whereby a~ueous solutions o~ the polyvinylpyrrolidone and the amine-c~nt~;n~n~ polymer are mixed with the emulsion ~ont~;n;ng the acrylic acid-contA;n;ng or methacrylic acid-contA; n; ng polymer. Although the scope of the present invention is not to be limited to any theoretical reasoning, it is believed that the acid moieties in the acrylic acid-containing or methacrylic acid-contA;n;ng polymer become co-crosslin~ed with the polyvinylpyrrolidone by the amine-contAi n~ ny polymer. Such reaction also is a competition reaction between the acid groups of the ring Sl.~vS 111 ~JTE SHEET (RULE 26) WO 97133645 PCT~US97/03402 opened polyvinylpyrrolidone an~ the acid group~ o~ the acrylic acid-containing polymer or methacrylic acid-con~;nln~ polymer with the amine-cont~;n;ng polymer. In addition, the addition o~ the acrylic acid-cont~tn~ng polymer slows the rate of gelation of the polyvinylpyrrolidone by the polyamine. Thus, gelation of the resulting composition occurs over a period of minutes, a~ opposed to an almost instantaneous gelation. Therefore, one may use conventional coating equipment for forming the adhesive composition, and then drying the product.
The polyvinylpyrrolidone, acrylic acid-cont~in;n~
polymer or methacrylic acid-cont~n~ng polymer and amine-cont~;n~ng polymer are present in amounts which enable co-cro~glinking of the acid moieties of the polyvinylpyrrolidone and of the acrylic acid-cont~, n; n~
polymer or methacrylic acid-cont~in;ng polymer with the amine-~ntAln;ng polymer. In general, the polyvinylpyrrolidone and amine-cont~;n;ng polymer are present in the composition at a weight ratio o~
polyvinylpyrrolidone to amine-cont~;n;ng polymer of ~rom about 40:1 to 150:1, pre~erably ~rom about 60:1 to about 80:1, and the acrylic acid-cont~in;ng polymer or methacrylic acid-cont~;ning polymer is present in the composition at a weight ratio of polyvinylpyrrolidone to acrylic acid-cont~in~ng polymer or methacrylic acid-cont~; n; ng polymer of from about 8:1 to about 16:1, preferably from about 10:1 to about 16:1. Upon mixing of the above-mentioned components, an adhesive composition is formed which is not soluble in water, yet is capable of ab~orbing from about 3 to 10 times its own weight in water when dried. Such composition has improved tack or stickiness. The composition has a cohesiveness to itself which is greater than the adhesiveness to the object or body to which it is adhered. Thus, the adhesive may be peeled readily ~rom the object or the body without damage or injury to the object or body.
S~l~S 11 ~ ~JTE SHEET (RULE 26) W O 97/3364S PCTrUS97/03402 In one embodiment, the compo~ition ~urther includes a plasticizer. Examples of plasticizers which may be employed include, but are not limited to, polyalkylene glycols such as polyethylene glycol and glycerine. Such plasticizers prevent drying of the adhesive and increase the tack. In one embodiment, the plasticizer is polyethylene glycol. The polyethylene glycol may have a molecular weight of ~rom about 100 to about 600, preferably at about 300. The polyethylene glycol typically has a melting point o~ from about 20~C to about 25~C at a molecular weight of 600, and has a melting point below -10~C at a molecular weight of 300. In general, the polyethylene glycol is added at a ratio of polyvinylpyrrolidone/polyethylene glycol of from about 0.5:1 to about 2:1, preferably from about 0.8:1 to about 1 : 1 .
In another embo~m~nt, the composition further includes a water-soluble tackifier. Examples of water-soluble tacki~iers which may be employed include, but are not limited ~o, polyvinylethers such as polymethylvinylether and polyvinylpyrrolidone having no ring opened groups.
In yet another embodiment, the composition may further include a surfactant, such as a phospholipid surfactant or other surfactants that provide antibacterial stabilizing propertie~ to the composition.
The composition of the present invention is useful in a wide variety o~ systems involving application to ~ni~l bodies, including especially human bodies. These include medical systems such as an adhesive for surgical drape~, wound and burn dressings and packings, bandages, plasters, transdermal drug delivery devices, and antimicrobial barriers for catheter hubs.
In a wound or burn dressing or packing, for example, in addition to the incorporation of a plasticizer and ~urfactant in the composition, the product may also contain a bactericide such as chlorhexidine gluconate, silver or copper compounds l-ke silver sulfadiazine, silver apacide SU~Ill~TE SHEET(RULE 26) W O 97/33645 PCT~US97/03402 and copper apaci~e, or an antibiotic or other ~nt;m;cro~ial The composition may also cont~;n enough sodium chloride to match physiological saline in order to prevent osmotic pumping ~rom the wound, and agents to promote regrowth of tissue. Wound or burn dressings and packings generally involve a releasable thermally ~ormed plastic receptacles ~or holding the compo~ition and a polymeric film, suc~ as polyurethane film, backing to control moisture-vapor transmission.
The composition may be used to attach a medical device to the body. In this case the aqueous gel may cont~i n, in addition to the tacki~ying plasticizer, an ~nt;m;crobial agent. When used as an adhesive to attach a catheter, such as a central venous catheter or intravenous catheter, it cover~ the hub providing an antimicrobial barrier to in~ection. The tacky composition may also be used to attach ostomy products to the body In a transdermal drug delivery system, the composition of the present invention will cont~ i n, in addition to the plasticizer, skin absorption agents like alcohols and amides, and at least one bioef~ecting drug. Examples of drugs that may be incorporated in such a system are nitroglycerine, pilocarpine, scopo- ~m; ne, clonidine, ~entanyl, nicotine, fen~luramine, phenterimine, phenylpropanolamine, theophylline, lidocaine, benzocaine, capsaicin, nicotinates, ergotamine tartrate, miconazole nitrate, salicylates such as choline salicylate, methyl salicylate, and the like. Such drugs may be added to the composition in an amount up to about 10~ by weight.
An electrolyte salt may be included in the composition to render it conductive for use in attaching electrocardiogram electrodes, transcutaneous electrical nerve stimulator electrodes, electro-surgical unit electrodes, bio-~eedback electrodes and iontophoresis drug delivery electrodes and de~ibrillation pads. Potassium chloride, sodium chloride sodium acetate, and magnesium acetate are examples o~ suitable electrolyte salts. Such ~alts may be present in the composition in an amount SUBSTITUTE SHEET (RULE 25) W O 97/33645 PCTrUS97/03402 between about 1 and about 20~, by weight, preferably about 2 and about 10~. The electrolyte salt may be incorporated in the reaction mixture at or about the time~that the ring opened PVP and amine-cont~i ni n~ polymer are mixed, preferably as by adding it to the water prior to dissolving the ring opened PVP. The conductive composition may al~o cs~t~n bioeffec~ive material for iontophoresis drug delivery.
In addition, the electrolyte ~alts herP~n~hove descri~ed, as well as carbon black or metal powders ~uch as copper powder, may be included in the adhesive composition to ~orm a conductive adhesive, a static dissipative adhesive, or an anti-static adhesive for closure strips for the packaging of sensitive electronic components such as computer chips, for example, or of photographic and x-ray films. Such compo~itions possess ade~uate conductivity as well as good adhesiveness. Such an adhesive yet conductive composition also may be employed in clean room dirt removal mats, whereby the adhesive fonms the top surface of the clean room mat, and retains dirt particles and metal particles.
The invention now will be described with respect to the examples; however, the scope of the present invention i8 not intended to be limited there}:)y.
Example 1 A two-part system was made of Part A and Part B. Part A contained 50.35g of a 20~ wt./wt. polyvinylpyrrolidone solution (with ring opened pyrrolidone groups), 3.0g pota~sium chloride, 24g SDA40 ethyl alcohol and 1.25g Gelva A~ 259, which is an acrylic polymer but not having any acid groups present. Part B consisted of 12.0g polyethyle~e glycol 300, 21.1g SDA40 ethyl alcohol, and 1.40g of a 12.5~
solids solution of polyethyl~n~;m;nP. The two parts were added to each other, mixed rapidly, and poured in the nip of a knife coater which had a release liner and a gap setting of 21 mils. Before the liner wa~ pulled through fully, the gel had formed. The coated liner was then dried in an oven with high air flow at 110~C. The dried product SUt~S ~ JTE SHEET (RULE 26) W O 97/33645 PCTrUS97/03402 wa~ 2 mils thick, had good dry tack and had resistance of 10 ohms. The ~ilm, however, was not uni~orm because it gelled before being pulled through the nip.~
~ Example 2 A two-part ~ystem was made o~ Part A and Part B. Part A cont~1 n~ 50.41g of a 20~ polyvinylpyrrolidone solution wt/wt., 20g of SDA40 ethyl alcohol, 3.0g potassium chloride, and 1.30g o~ Gelva 2484 (an acid co~t~in;n~
acrylic acid ester adhesive) emulsion. Gelva 2484 is an acrylic acid ester and acrylic acid-cont~;n~ng terpolymer from Monsanto including acrylic acid, butyl acrylate, and 2-ethyl hexyl acrylate. Part B consisted of 12.12g polyethylene glycol 300, 20g of S~A40 ethyl alcohol and 1.27g of 12.5~ polyethylene~m;n~ solution. The two parts were combined, mixed and poured into the nip of a knife over roller coater in which wa~ a release liner, gap set ~or 21 mils. The liner was pulled through the coater.
After removal, excess coating dripped for about 15 seconds ~efore gelation started. The coating on the release liner was dried in an oven with high air flow at 110~C for 5 minutes. The resulting 2 mil coating had excellent d~y tack and good resistivity.
Example 3 A two-part system was made of Part A and Part B. Part A cont~;ne~ 50.35g 20~ polyvinylpyrrolidone solution, 3g pota~sium chloride, 25g S~A40 ethyl alcohol and 1.30g Gelva 2397 adhesive, which is an acrylic acid ester and acrylic acid-cont~ n; ng terpolymer having the compo~Pnt~
here;n~hove described, and which has a higher acrylic acid content that Gelva 2484. Part B contained 12.12g polyethylene glycol 300, 1.27g 12.5~ polyethylen~;m;n~
solution, and 20g SDA40 ethyl alcohol. Parts A and B were combined, mixed and poured into the nip of a knife over a roll coater which had a release liner in the nip. The release liner was pulled through and the excess material dripped for more than 30 seconds before gelation started.
SUBSTITUTE SHEET (RULE 26) W O 97/33645 PCT~US97/03402 The coating was dried in an oven with high air ~low at 110~
~or 5 minutes. The 2 mil coating had excellent tack a~d resi~tivity.
Example 4 A two-part system was made of Part A and Part B. Part A consisted of a mixture which was in a ratio of 50.34g 20 polyvinylpyrrolidone (with partial ring opened groups~, 25.31g SDA40 ethyl alcohol and 1.30g Gelva 2333 adhesive (an acrylic adhesive, including an acrylic acid ester alld acrylic acid-cont~n;ng terpolymer having the components here;n~hove described, with an acid content between Gel~a 2484 and Gelva 2397), and 3g of potassium chloride. Part B was a mixture of 12.17g polyethylene glycol 300, 1.27g of a 12.5~ solution o~ polyethyl~n~neim~ne and 20.21g SDA40 ethyl alcohol. The solutions of both parts were placed in separate tanks and were ed separately by two gear pumps to a static mixer (3 elements, 2~" long, 5/8" thick). The combined mixture was fed to the nip of a roll coater with a spreader bar through which a ~on~l~ctive release liner was passing. The width o~ the coater is 14" after the coater it went into a dryer oven with 3 zone heating and good air flow. The liner was be ng pulled at about 50 ~t/min. At the exit of the dryer a second "easy release" liner was placed over the dried adhesive. The 14" wide web was slit to 3" wide and tested as a sealing tape ~or a package ~or elertronic chips. It was ~ound to have good adhesive properties and to pre~ent static charge build-up.
Example 5 A two-part system was made o~ Part A and Part B. Part A cont~; n~ 50.35 gms of a 20~ polyvinylpyrrolidone with some ring opened pyrrolidone groups, 24gms SDA40 ethyl alcohol, 1.03gms o~ a 33% solution o~ polyvinyl methylether and 1.25gms o~ Gelva AE259. Part B cont~; nP~ 12.0g~s polyethylenglycol, 25 yms of SDA40 ethyl alcohol, and 1.30gms 12.5% polyethyleneimine. The two parts were mixed together, ~tirred, and then q~ickly poured into the nip of a kni~e over a roll coater with a gap of 21 mils and in which a release liner was placed. The liner was pulled SU~5 1 1 1 UTE SHEET [RULE 26) through the gap and gelation occurred in the process o~
pulling. The coating on the release liner was placed in an oven with high air fiow and heated at 110~C - It was dried ~or 15 minutes. A~ter cooling it was tested for dry and wet tack. It had adequate dry tack but poor wet tack. The coating appeared to be non-uniform.
This illustrate~ the ~onmation of a pressure-sensitive adhesive that does not contain any free acid groups in the backbone of the acrylic acid-cont~;ng polymer.
Example 6 A two-part system was made of Part A and Part B. Part A cont~;n~ 50.41g of a 20~ polyvinylpyrrolidone solution (cont~n;n~ ring opened pyrrolidone groups) 22grams of SDA40 ethyl alcohol, 1.30 grams of Gelva 2484, and 1.24g of a 20% solution of po~ymethylvinylether in water. Part B
co~t~;nPd 12.18g polyethylene glycol 300, 23 grams of SD~40 ethyl alcohol, and 1.10 grams of 12.5~ polyethyl~ne;m;ne.
The two parts were com~ined, stirred and poured into the nip of a knife over a roller coater set at 21 mil gaps in which was a release liner. The liner with the coating was pulled through. Excess coating began to drip tl,. ouyh the gap and after about 15 seconds began to gel.
The liner with the coating was placed in an oven with high air flow at 110~C ~or 15 minutes. After cooling it wa~ lAm;n~ted to a thin film polyurethane o~ about 1 mil thickness. Samples were tested by ~e~nvving the release liner from strips and dry and wet tack were determined.
The sample was equivalent in dry tack to ~xample 5 ~ut had much better wet tack.
Exam~le 7 A two-part system was made 0c Part A and Part B. Part A cont~;nP~ 50.35 gram~ of 20~ polyvinylpyrrolidone, 23.60 grams SDA40 ethyl alcohol, ~.30 grams Gelva 2397 emulsion adhesive cont~i n; ng unneutralized acid groups in the backbone, and 1.56g of a 20~ solution of polymethylvinylether in water. Part B contained 12.12 grams of polyethylene g ycol 300, 20 grams of SDA40 ethyl alcohol and 1.01 grams of a 12.5~ polyethyl~ne~m;ne in SUBSTITUTE SHEET(RULE 26) W O 97/33645 PCTrUS97/03402 water. Part B was added to Part A and ~uickly stirred and ~e~ to the nip o a knife over a roll coater with a gap of 21 mils in which was a release liner. The liner was pulled through the gap depositing a film of the coating.
After removal, excess coating dripped from the gap and did not start to gel for about 1 minute. The liner with the coating was placed in an o~en with high air ~low at 110~C
~or 15 minutes. After removal it was allowed to cool and then ~Am;n~ted to a polyurethane film. A stAn~Ard peel adhesion of this Eilm with adhesive against stainless steel was measured at 350-500 grams. It had good adhesion to wet skin but was painlessly peeled from the skin.
Example 8 A two-part system was made of Part A and Part B. Part A contained 49.~3 grams 20% polyvinylpyrrolidone with partial ring opened pyrrolidone groups, 25.09g SDA40 ethyl alcohol, and 1.58g Gelva 2333 emulsion adhesive. Part B
cont~n~A 1.27g polyethyl~ne;~n~, 20.79g SDA40 ethyl alcohol and 8.85g polyethylene glycol 300. Part B was added to Part A, stirred and then ~uickly added to the nip of a knife over a roller coater, having a gap o~ 21 mils with a release liner in the gap. The release liner wa~
pulled through and after it cleared the gap excess coating began dripping down. After a~out 30 seconds the coating solution began to gel. Ti1e coating on the release liner was placed in an oven with high air ~low and at a temperature o~ llO~C. A~ter 15 minutes the liner with the coating was removed and allowed to cool. It was lAm~nAted to a thin ~ilm urethane. It had good adhesion to the urethane film. Testing of the film lAm~nAted adhesive showed it had good adhesion to wet or damp skin but did not have as good d~y tack as in Example 7.
Example 9 S~ 111 ~JTE SHEET (RULE 26) W O 97/3364~ PCTAUS97/03402 ~ ach of Formulations A, B, and C were made, havinq the ~ollowing components:
Part A
50g ~ 20% polyvinylpyrrolidone 48g H2O
1.3g 20~ polymethylvinylether (PVM) in water 0.08g sodium C14-C16 olefin sulfonate surfactant Part B
12g polyethylene g~ycol 12g H2O
l.Og 12.5~ polyethylPne~m7ne in H20 Formulation A had no adhesive com~onent added. Formulation B ~urther included 1.3g of Gelva 2484 in Part A.
Formulation C further included 1.3g of Gelva 2333 in Part A.
For each formulation, Part ~ was added to Part A, and each ~ormulation was stirred. Subsequent to stirring, each fonmulation was poured onto an interface of a wire wound stainless steel rod and glass. The rod then is rolled along the glass sur~ace as the formulation is being applied, thereby ~orming a coating o~ each ~ormulation on a glass sur~ace. Each o~ Formulations A, B, and C then was dried at 105~C ~or 15 minutes, and then covered with a polye~ter film. One-inch stxips then were cut, and the adhesion of polyester to glass for each ~ormulation was measured. The adhesion for each formulation was as follow~:
Formulatio7l A - 1.1 oz./in.
Fonmulatio~ B - 3.7 oz./in.
Formulation C - 4.5 o~./in.
It is to be understood, however, that the scope of the present invention is not to be limited to the speci~ic embodiments described above. The invention may be practiced other than as particularly described above. The invention may be practiced other than as particularly described and still be within the scope of the accompanying claims.
S~DBSTITUTE SHEET (RULE 26)
Claims (26)
1. A composition comprising a cross-linked salt of:
(a) a polyvinylpyrrolidone having ring opened pyrrolidone groups;
(b) at least one acrylic acid-containing or methacrylic acid-containing polymer; and (c) an amine-containing polymer, wherein said polyvinylpyrrolidone and said amine-containing polymer are present in said composition at a weight ratio of polyvinylpyrrolidone to amine-containing polymer of from about 40:1 to about 150:1, and said acrylic acid-containing polymer or methacrylic acid - containing polymer is present in said composition at a weight ratio of polyvinylpyrrolidone to acrylic acid-containing polymer or methacrylic acid-containing polymer of from about 8:1 to about 16:1.
(a) a polyvinylpyrrolidone having ring opened pyrrolidone groups;
(b) at least one acrylic acid-containing or methacrylic acid-containing polymer; and (c) an amine-containing polymer, wherein said polyvinylpyrrolidone and said amine-containing polymer are present in said composition at a weight ratio of polyvinylpyrrolidone to amine-containing polymer of from about 40:1 to about 150:1, and said acrylic acid-containing polymer or methacrylic acid - containing polymer is present in said composition at a weight ratio of polyvinylpyrrolidone to acrylic acid-containing polymer or methacrylic acid-containing polymer of from about 8:1 to about 16:1.
2. The composition of Claim 1 wherein said polyvinylpyrrolidone has ring opened pyrrolidone groups which provide at lease 1.5 x 10-2 milliequivalents of carboxylic acid groups per gram of polymer.
3. The composition of claim 1 wherein said amine-containing polymer is selected from the group consisting of polyethyleneimine, amine-terminated polyethylene oxide, amine-terminated polyethylene/polypropylene oxide, polymers of dimethyl amino ethyl methacrylate, and copolymers of dimethyl amino ethyl methacrylate and vinyl pyrrolidone.
4. The composition of Claim 3 wherein said amine-containing polymer is polyethyleneimine.
5. The composition of Claim 1 wherein said polyvinylpyrrolidone has a K-value of at least 50.
6. The composition of Claim 1 wherein said at least one acrylic acid-containing polymer or methacrylic acid-containing polymer is a terpolymer including acrylic acid and acrylic acid esters or a terpolymer including methacrylic acid and methacrylic acid esters.
7. The composition of Claim 6 wherein said terpolymer is a terpolymer of acrylic acid, butyl acrylate, and 2-ethyl hexyl acrylate.
8. The composition of Claim 1 wherein said at least one acrylic acid-containing polymer or methacrylic acid-containing polymer is a terpolymer of acrylic acid or methacrylic acid, butadiene, and styrene.
9. The composition of Claim 1 and further comprising a plasticizer.
10. The composition of Claim 9 wherein said plasticizer is selected from the group consisting of polyalkylene glycols and glycerine.
11. The composition of Claim 10 wherein said plasticizer is polyethylene glycol.
12. The composition of Claim 1 and further comprising an electrolyte salt.
13. The composition of Claim 12 wherein said electrolyte salt is selected from the group consisting of potassium chloride, sodium chloride, sodium acetate, and magnesium acetate.
14. The composition of Claim 13 wherein said electrolyte salt is sodium acetate.
15. In a system for adhesion to an animal body or an object, wherein said system includes an adhesive, the improvement wherein said adhesive comprises the composition of Claim 1.
16. The composition of Claim 11, and further comprising a water soluble tackifying agent.
17. The composition of Claim 16 wherein said tackifying agent is polymethylvinylether.
18. The composition of Claim 16 wherein said tackifying agent is a polyvinylpyrrolidone having no ring opened pyrrolidone groups.
19. A hydrogel pressure sensitive adhesive for attaching a wound dressing to skin including the composition of Claim 17.
20. A transdermal drug delivery system, said system including:
(a) a hydrogel pressure sensitive adhesive including the composition of Claim 17; and (b) at least one drug.
(a) a hydrogel pressure sensitive adhesive including the composition of Claim 17; and (b) at least one drug.
21. A conductive hydrogel pressure sensitive adhesive for closure strips employed in the packaging of electronic components, said adhesive including the composition of Claim 13.
22. A conductive hydrogel pressure sensitive adhesive for attaching an electrode to skin including the composition of Claim 13.
23. A conductive hydrogel pressure sensitive adhesive for a dirt removal mat for clean room use, said adhesive including the composition of Claim 13.
24. A conductive hydrogel pressure sensitive adhesive for iontophoretic drug delivery devices including the composition of Claim 13, and further including at least one bioeffective drug.
25. The composition of Claim 1 wherein said polyvinylpyrrolidone and said amine-containing polymer are present in said composition at a weight ratio of polyvinylpyrrolidone to amine-containing polymer of from about 60:1 to about 80:1.
26. The composition of Claim 1 wherein said polyvinylpyrrolidone and said acrylic acid-containing polymer or said methacrylic acid-containing polymer are present in said composition at a weight ratio of polyvinylpyrrolidone to acrylic acid-containing polymer or methacrylic acid-containing polymer of from about 10:1 to about 16:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/615,624 US5645855A (en) | 1996-03-13 | 1996-03-13 | Adhesive compositions including polyvinylpyrrolidone acrylic acid polymers, and polyamines |
| US08/615,624 | 1996-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2247431A1 true CA2247431A1 (en) | 1997-09-18 |
Family
ID=24466189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002247431A Abandoned CA2247431A1 (en) | 1996-03-13 | 1997-02-19 | Adhesive compositions including polyvinylpyrrolidone, acrylic acid polymers, and polyamines |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5645855A (en) |
| EP (1) | EP0891202A4 (en) |
| CA (1) | CA2247431A1 (en) |
| WO (1) | WO1997033645A1 (en) |
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| US4906475A (en) * | 1988-02-16 | 1990-03-06 | Paco Pharmaceutical Services | Estradiol transdermal delivery system |
| US5306504A (en) * | 1992-12-09 | 1994-04-26 | Paper Manufactures Company | Skin adhesive hydrogel, its preparation and uses |
-
1996
- 1996-03-13 US US08/615,624 patent/US5645855A/en not_active Expired - Fee Related
-
1997
- 1997-02-19 WO PCT/US1997/003402 patent/WO1997033645A1/en not_active Application Discontinuation
- 1997-02-19 EP EP97908870A patent/EP0891202A4/en not_active Withdrawn
- 1997-02-19 CA CA002247431A patent/CA2247431A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5645855A (en) | 1997-07-08 |
| WO1997033645A1 (en) | 1997-09-18 |
| EP0891202A1 (en) | 1999-01-20 |
| EP0891202A4 (en) | 2000-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |